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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): m482.
Published online 2010 March 31. doi:  10.1107/S1600536810011384
PMCID: PMC2983778

(2-{[1,1-Bis(hydroxy­meth­yl)-2-oxidoeth­yl]imino­meth­yl}-4-chloro­phenolato-κ3 N,O,O′)dibutyl­tin(IV)

Abstract

The Schiff base ligand in the title compound, [Sn(C4H9)2(C11H12ClNO4)], chelates to the Sn atom through the two deprotonated O atoms, as well as through the N atom, to confer an overall cis-C2SnNO2 trigonal-bipyramidal geometry at tin [C—Sn—C = 130.3 (1)°]. The hydr­oxy groups engage in O—H(...)O hydrogen bonding with the O atoms of adjacent mol­ecules, generating a chain running along the c axis.

Related literature

For the crystal structure of the uncoordinated Schiff base, see: Ng (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m482-scheme1.jpg

Experimental

Crystal data

  • [Sn(C4H9)2(C11H12ClNO4)]
  • M r = 490.58
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m482-efi1.jpg
  • a = 18.6212 (2) Å
  • b = 13.4657 (2) Å
  • c = 16.6949 (1) Å
  • β = 91.845 (1)°
  • V = 4184.03 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.37 mm−1
  • T = 123 K
  • 0.43 × 0.30 × 0.25 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.590, T max = 0.726
  • 23501 measured reflections
  • 4803 independent reflections
  • 4350 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.020
  • wR(F 2) = 0.064
  • S = 0.94
  • 4803 reflections
  • 243 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.60 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011384/bt5229sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011384/bt5229Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The Schiff base derived from the condensation of salicylaldehyde (and other substituted salcylaldehydes) and tris(hydroxymethyl)methylamine is invariably deprotonated with respect to the phenoxy hydrogen atom and the deprotonated ligand binds to a metal atom through this oxygen atom. Occasionally, one of the methylelenehydroxy groups is also deprotonated in the metal complexes. The 4-chloro substituted compound, which exists as a zwitterion (Ng, 2008), when reacted with dibutyltin oxide is doubly-deprotonated in order to balance the charge of tin so that the ligand binds in a terdentate manner (Scheme I, Fig. 1).

The tin atom shows cis-trigonal bipyramidal coordination with a C–Sn–C angle of 130.3 (1) °; the ligand spans the two axial sites. The C–Sn–C angle is not opened up by the electronegative atom of any adjacent molecule. Adjacent molecules are linked by hydrogen bonds to form a ribbon (Fig. 2).

Experimental

The Schiff base, 4-chloro-2-tris[(hydroxymethyl)methylimino]phenol was prepared from tris(hydroxymethyl)aminomethane and 5-chlorosalicylaldehyde in ethanol. The compound (0.26 g, 0.1 mmol) and dibutyltin oxide (0.25 g, 1.0 mmol) were heated in toluene in a Dean-Stark apparatus for 8 hours. Crystals was obtained when the filtered solution was allowed to evaporate over several days.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The hydroxy H-atoms were located in a difference Fourier map, and were refined isotropically with a distance restraint of O–H 0.84±0.01 Å.

Figures

Fig. 1.
Anisotropic displacement ellipsoid plot (Barbour, 2001) of Sn(C4H9)2(C11H12ClNO4) with ellipsoids at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Fig. 2.
Packing diagram of the title compound.

Crystal data

[Sn(C4H9)2(C11H12ClNO4)]F(000) = 2000
Mr = 490.58Dx = 1.558 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9381 reflections
a = 18.6212 (2) Åθ = 2.2–31.7°
b = 13.4657 (2) ŵ = 1.37 mm1
c = 16.6949 (1) ÅT = 123 K
β = 91.845 (1)°Block, yellow
V = 4184.03 (8) Å30.43 × 0.30 × 0.25 mm
Z = 8

Data collection

Bruker SMART APEX diffractometer4803 independent reflections
Radiation source: fine-focus sealed tube4350 reflections with I > 2σ(I)
graphiteRint = 0.025
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −24→24
Tmin = 0.590, Tmax = 0.726k = −15→17
23501 measured reflectionsl = −21→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 0.94w = 1/[σ2(Fo2) + (0.0487P)2 + 2.5005P] where P = (Fo2 + 2Fc2)/3
4803 reflections(Δ/σ)max = 0.001
243 parametersΔρmax = 0.60 e Å3
2 restraintsΔρmin = −0.31 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Sn10.324176 (5)0.374067 (8)0.254047 (6)0.01818 (5)
Cl10.05353 (3)0.31243 (4)−0.07291 (3)0.03821 (13)
N10.33156 (7)0.43789 (10)0.13234 (8)0.0169 (3)
O10.26803 (7)0.26136 (9)0.18945 (7)0.0251 (3)
O20.39660 (6)0.49305 (9)0.27014 (7)0.0213 (2)
O30.51910 (6)0.51554 (9)0.10309 (7)0.0208 (2)
O40.37037 (6)0.56261 (10)−0.01897 (7)0.0233 (3)
C10.40248 (10)0.27086 (14)0.29943 (12)0.0280 (4)
H1A0.44520.27570.26580.034*
H1B0.41750.29220.35420.034*
C20.38064 (11)0.16181 (15)0.30333 (12)0.0318 (4)
H2A0.36690.13910.24860.038*
H2B0.42290.12240.32180.038*
C30.31878 (12)0.14046 (16)0.35828 (14)0.0367 (5)
H3A0.27610.17860.33920.044*
H3B0.30660.06900.35460.044*
C40.33487 (16)0.1662 (3)0.44466 (15)0.0629 (8)
H4A0.29300.15070.47650.094*
H4B0.34580.23720.44920.094*
H4C0.37630.12760.46460.094*
C50.23412 (10)0.43890 (15)0.31046 (12)0.0298 (4)
H5A0.24990.45970.36510.036*
H5B0.22040.49970.28040.036*
C60.16740 (12)0.37495 (16)0.31741 (16)0.0403 (5)
H6A0.15470.34690.26400.048*
H6B0.17890.31870.35380.048*
C70.10287 (11)0.42862 (17)0.34800 (15)0.0420 (5)
H7A0.08890.48140.30920.050*
H7B0.11680.46140.39930.050*
C80.03807 (14)0.3637 (2)0.36135 (19)0.0559 (7)
H8A−0.00080.40420.38220.084*
H8B0.05090.31140.40000.084*
H8C0.02210.33340.31040.084*
C90.22124 (9)0.27459 (12)0.12977 (9)0.0194 (3)
C100.16258 (9)0.20867 (13)0.11998 (10)0.0236 (3)
H100.15840.15440.15590.028*
C110.11135 (9)0.22152 (14)0.05944 (10)0.0245 (4)
H110.07100.17850.05570.029*
C120.11877 (9)0.29764 (13)0.00376 (10)0.0230 (3)
C130.17673 (10)0.36033 (13)0.00828 (11)0.0229 (4)
H130.18260.4098−0.03150.028*
C140.22784 (8)0.35110 (13)0.07241 (10)0.0186 (3)
C150.28649 (8)0.42135 (12)0.07342 (10)0.0181 (3)
H150.29250.45910.02610.022*
C160.38984 (8)0.51236 (12)0.12515 (9)0.0159 (3)
C170.39581 (9)0.56345 (12)0.20768 (9)0.0192 (3)
H17A0.44040.60340.21120.023*
H17B0.35460.60900.21360.023*
C180.45807 (8)0.45272 (12)0.10880 (10)0.0180 (3)
H18A0.46670.40420.15260.022*
H18B0.45100.41520.05810.022*
C190.37587 (9)0.59373 (13)0.06223 (10)0.0201 (3)
H19B0.33070.62820.07520.024*
H19A0.41520.64310.06740.024*
H3O0.5441 (11)0.5129 (19)0.1452 (9)0.043 (7)*
H4O0.4099 (8)0.5403 (17)−0.0338 (13)0.036 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn10.01691 (8)0.02207 (8)0.01539 (8)−0.00301 (4)−0.00201 (5)0.00291 (4)
Cl10.0319 (2)0.0357 (3)0.0454 (3)−0.00971 (19)−0.0231 (2)0.0064 (2)
N10.0143 (6)0.0188 (7)0.0176 (6)−0.0016 (5)0.0002 (5)0.0011 (5)
O10.0287 (6)0.0245 (6)0.0215 (6)−0.0075 (5)−0.0081 (5)0.0056 (5)
O20.0235 (6)0.0246 (6)0.0157 (5)−0.0051 (5)−0.0039 (4)0.0021 (5)
O30.0147 (5)0.0293 (7)0.0184 (6)−0.0050 (4)−0.0022 (4)0.0037 (5)
O40.0210 (6)0.0322 (7)0.0165 (6)0.0003 (5)0.0003 (5)0.0036 (5)
C10.0220 (8)0.0282 (10)0.0334 (10)−0.0012 (7)−0.0055 (7)0.0062 (8)
C20.0328 (10)0.0266 (10)0.0355 (10)0.0011 (8)−0.0034 (8)0.0027 (8)
C30.0356 (11)0.0367 (11)0.0372 (12)−0.0116 (8)−0.0060 (9)0.0108 (9)
C40.0592 (17)0.094 (2)0.0357 (13)−0.0296 (16)−0.0015 (12)0.0084 (14)
C50.0264 (9)0.0296 (10)0.0337 (10)−0.0011 (7)0.0066 (7)−0.0002 (8)
C60.0269 (10)0.0461 (14)0.0485 (14)−0.0077 (8)0.0097 (9)−0.0149 (10)
C70.0303 (10)0.0395 (12)0.0570 (14)0.0044 (9)0.0120 (10)0.0132 (10)
C80.0296 (12)0.080 (2)0.0587 (17)−0.0080 (11)0.0091 (11)−0.0029 (13)
C90.0205 (8)0.0202 (8)0.0173 (7)−0.0016 (6)−0.0003 (6)−0.0012 (6)
C100.0286 (9)0.0232 (9)0.0189 (8)−0.0089 (7)0.0012 (7)0.0012 (6)
C110.0208 (8)0.0274 (9)0.0252 (9)−0.0083 (7)0.0013 (6)−0.0056 (7)
C120.0197 (8)0.0246 (9)0.0242 (8)−0.0015 (6)−0.0067 (6)−0.0025 (7)
C130.0225 (8)0.0224 (9)0.0234 (9)−0.0034 (6)−0.0059 (7)0.0036 (6)
C140.0166 (7)0.0208 (8)0.0183 (8)−0.0017 (6)−0.0020 (6)−0.0001 (6)
C150.0175 (7)0.0197 (8)0.0170 (7)−0.0016 (6)−0.0004 (6)0.0023 (6)
C160.0144 (7)0.0174 (8)0.0159 (7)−0.0027 (5)−0.0014 (5)0.0000 (6)
C170.0222 (8)0.0188 (8)0.0165 (7)−0.0009 (6)0.0000 (6)−0.0010 (6)
C180.0165 (7)0.0183 (8)0.0191 (7)−0.0018 (6)−0.0008 (6)0.0004 (6)
C190.0213 (8)0.0197 (8)0.0191 (8)0.0003 (6)−0.0011 (6)0.0025 (6)

Geometric parameters (Å, °)

Sn1—O12.118 (1)C6—C71.506 (3)
Sn1—O22.106 (1)C6—H6A0.9900
Sn1—C12.136 (2)C6—H6B0.9900
Sn1—C52.136 (2)C7—C81.513 (3)
Sn1—N12.215 (1)C7—H7A0.9900
Cl1—C121.7476 (17)C7—H7B0.9900
N1—C151.292 (2)C8—H8A0.9800
N1—C161.4852 (19)C8—H8B0.9800
O1—C91.314 (2)C8—H8C0.9800
O2—C171.4091 (19)C9—C101.413 (2)
O3—C181.4224 (18)C9—C141.415 (2)
O3—H3O0.831 (10)C10—C111.378 (2)
O4—C191.419 (2)C10—H100.9500
O4—H4O0.840 (10)C11—C121.394 (3)
C1—C21.526 (3)C11—H110.9500
C1—H1A0.9900C12—C131.370 (2)
C1—H1B0.9900C13—C141.415 (2)
C2—C31.523 (3)C13—H130.9500
C2—H2A0.9900C14—C151.445 (2)
C2—H2B0.9900C15—H150.9500
C3—C41.504 (3)C16—C191.534 (2)
C3—H3A0.9900C16—C181.535 (2)
C3—H3B0.9900C16—C171.541 (2)
C4—H4A0.9800C17—H17A0.9900
C4—H4B0.9800C17—H17B0.9900
C4—H4C0.9800C18—H18A0.9900
C5—C61.519 (3)C18—H18B0.9900
C5—H5A0.9900C19—H19B0.9900
C5—H5B0.9900C19—H19A0.9900
O2—Sn1—O1156.02 (5)C8—C7—H7A108.5
O2—Sn1—C191.30 (6)C6—C7—H7B108.5
O1—Sn1—C191.98 (6)C8—C7—H7B108.5
O2—Sn1—C598.13 (6)H7A—C7—H7B107.5
O1—Sn1—C597.80 (6)C7—C8—H8A109.5
C1—Sn1—C5130.26 (8)C7—C8—H8B109.5
O2—Sn1—N176.31 (5)H8A—C8—H8B109.5
O1—Sn1—N181.67 (5)C7—C8—H8C109.5
C1—Sn1—N1121.08 (6)H8A—C8—H8C109.5
C5—Sn1—N1108.59 (7)H8B—C8—H8C109.5
C15—N1—C16120.89 (13)O1—C9—C10119.58 (15)
C15—N1—Sn1125.01 (11)O1—C9—C14122.82 (14)
C16—N1—Sn1113.79 (9)C10—C9—C14117.57 (14)
C9—O1—Sn1126.37 (11)C11—C10—C9121.35 (16)
C17—O2—Sn1115.22 (9)C11—C10—H10119.3
C18—O3—H3O110.1 (17)C9—C10—H10119.3
C19—O4—H4O110.5 (16)C10—C11—C12120.03 (15)
C2—C1—Sn1117.49 (12)C10—C11—H11120.0
C2—C1—H1A107.9C12—C11—H11120.0
Sn1—C1—H1A107.9C13—C12—C11120.74 (15)
C2—C1—H1B107.9C13—C12—Cl1119.85 (14)
Sn1—C1—H1B107.9C11—C12—Cl1119.40 (13)
H1A—C1—H1B107.2C12—C13—C14119.79 (16)
C3—C2—C1114.53 (17)C12—C13—H13120.1
C3—C2—H2A108.6C14—C13—H13120.1
C1—C2—H2A108.6C9—C14—C13120.36 (15)
C3—C2—H2B108.6C9—C14—C15123.44 (14)
C1—C2—H2B108.6C13—C14—C15116.18 (15)
H2A—C2—H2B107.6N1—C15—C14126.46 (15)
C4—C3—C2113.76 (19)N1—C15—H15116.8
C4—C3—H3A108.8C14—C15—H15116.8
C2—C3—H3A108.8N1—C16—C19115.43 (12)
C4—C3—H3B108.8N1—C16—C18105.80 (12)
C2—C3—H3B108.8C19—C16—C18112.02 (13)
H3A—C3—H3B107.7N1—C16—C17105.13 (12)
C3—C4—H4A109.5C19—C16—C17107.40 (13)
C3—C4—H4B109.5C18—C16—C17110.87 (12)
H4A—C4—H4B109.5O2—C17—C16111.11 (13)
C3—C4—H4C109.5O2—C17—H17A109.4
H4A—C4—H4C109.5C16—C17—H17A109.4
H4B—C4—H4C109.5O2—C17—H17B109.4
C6—C5—Sn1117.23 (14)C16—C17—H17B109.4
C6—C5—H5A108.0H17A—C17—H17B108.0
Sn1—C5—H5A108.0O3—C18—C16111.62 (13)
C6—C5—H5B108.0O3—C18—H18A109.3
Sn1—C5—H5B108.0C16—C18—H18A109.3
H5A—C5—H5B107.2O3—C18—H18B109.3
C7—C6—C5114.67 (17)C16—C18—H18B109.3
C7—C6—H6A108.6H18A—C18—H18B108.0
C5—C6—H6A108.6O4—C19—C16116.64 (14)
C7—C6—H6B108.6O4—C19—H19B108.1
C5—C6—H6B108.6C16—C19—H19B108.1
H6A—C6—H6B107.6O4—C19—H19A108.1
C6—C7—C8114.9 (2)C16—C19—H19A108.1
C6—C7—H7A108.5H19B—C19—H19A107.3
O2—Sn1—N1—C15−163.22 (14)C9—C10—C11—C123.4 (3)
O1—Sn1—N1—C1526.37 (13)C10—C11—C12—C130.1 (3)
C1—Sn1—N1—C15113.65 (14)C10—C11—C12—Cl1179.67 (14)
C5—Sn1—N1—C15−69.11 (15)C11—C12—C13—C14−3.2 (3)
O2—Sn1—N1—C1610.39 (10)Cl1—C12—C13—C14177.18 (14)
O1—Sn1—N1—C16−160.03 (11)O1—C9—C14—C13178.46 (16)
C1—Sn1—N1—C16−72.75 (12)C10—C9—C14—C130.4 (2)
C5—Sn1—N1—C16104.50 (11)O1—C9—C14—C150.4 (3)
O2—Sn1—O1—C9−64.26 (19)C10—C9—C14—C15−177.68 (16)
C1—Sn1—O1—C9−161.94 (14)C12—C13—C14—C93.0 (3)
C5—Sn1—O1—C966.95 (14)C12—C13—C14—C15−178.85 (16)
N1—Sn1—O1—C9−40.81 (13)C16—N1—C15—C14179.74 (15)
O1—Sn1—O2—C1741.07 (18)Sn1—N1—C15—C14−7.1 (2)
C1—Sn1—O2—C17138.89 (12)C9—C14—C15—N1−14.7 (3)
C5—Sn1—O2—C17−90.09 (12)C13—C14—C15—N1167.15 (17)
N1—Sn1—O2—C1717.16 (10)C15—N1—C16—C1923.6 (2)
O2—Sn1—C1—C2−179.95 (15)Sn1—N1—C16—C19−150.32 (11)
O1—Sn1—C1—C2−23.71 (15)C15—N1—C16—C18−100.89 (16)
C5—Sn1—C1—C278.25 (18)Sn1—N1—C16—C1885.21 (12)
N1—Sn1—C1—C2−105.17 (15)C15—N1—C16—C17141.72 (15)
Sn1—C1—C2—C3−62.2 (2)Sn1—N1—C16—C17−32.18 (14)
C1—C2—C3—C4−61.8 (3)Sn1—O2—C17—C16−41.23 (15)
O2—Sn1—C5—C6−176.69 (16)N1—C16—C17—O246.68 (16)
O1—Sn1—C5—C621.30 (17)C19—C16—C17—O2170.11 (12)
C1—Sn1—C5—C6−78.01 (19)C18—C16—C17—O2−67.21 (16)
N1—Sn1—C5—C6105.09 (17)N1—C16—C18—O3−178.13 (12)
Sn1—C5—C6—C7−172.58 (17)C19—C16—C18—O355.30 (17)
C5—C6—C7—C8−175.3 (2)C17—C16—C18—O3−64.66 (16)
Sn1—O1—C9—C10−146.41 (13)N1—C16—C19—O4−64.69 (18)
Sn1—O1—C9—C1435.5 (2)C18—C16—C19—O456.47 (18)
O1—C9—C10—C11178.29 (16)C17—C16—C19—O4178.44 (13)
C14—C9—C10—C11−3.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3o···O2i0.83 (1)1.79 (1)2.612 (2)172 (3)
O4—H4o···O3ii0.84 (1)1.94 (1)2.739 (2)160 (2)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5229).

References

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  • Westrip, S. P. (2010). publCIF In preparation.

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